U.S. patent number 3,832,418 [Application Number 05/249,194] was granted by the patent office on 1974-08-27 for isobutylene dimerization process.
This patent grant is currently assigned to Gulf Research & Development Company. Invention is credited to Paul G. Bercik, Alfred M. Henke.
United States Patent |
3,832,418 |
Bercik , et al. |
August 27, 1974 |
ISOBUTYLENE DIMERIZATION PROCESS
Abstract
A process for selectively dimerizing isobutylene contained in a
C.sub.4 olefin mixture employing a catalyst composition comprising
a presulfided Group VI or Group VIII metal deposited on an acidic,
amorphous silica-alumina support.
Inventors: |
Bercik; Paul G. (Trafford,
PA), Henke; Alfred M. (Springdale, PA) |
Assignee: |
Gulf Research & Development
Company (Pittsburgh, PA)
|
Family
ID: |
22942428 |
Appl.
No.: |
05/249,194 |
Filed: |
May 1, 1972 |
Current U.S.
Class: |
585/515; 502/219;
502/222 |
Current CPC
Class: |
C07C
2/24 (20130101); B01J 23/74 (20130101); C07C
2/24 (20130101); B01J 37/20 (20130101); C07C
11/02 (20130101); C07C 2521/12 (20130101); C07C
2523/755 (20130101) |
Current International
Class: |
C07C
2/00 (20060101); B01J 23/74 (20060101); B01J
37/00 (20060101); B01J 37/20 (20060101); C07C
2/24 (20060101); C07c 003/10 () |
Field of
Search: |
;260/683.15R,683.15B,677R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Coughlan, Jr.; Paul M.
Claims
We claim:
1. A process for the selective dimerization of isobutylene which
consists essentially of contacting a mixture of C.sub.4
mono-olefins containing isobutylene under dimerization conditions
with a sulfided catalyst composition consisting essentially of 0.5
to 20 weight percent of nickel and 0 to 5.0 weight percent fluorine
on an acidic amorphous silica-alumina support, said support
comprising from 50 to 90 weight percent silica, said sulfided
catalyst containing at least 0.5 mol of sulfur per mol of nickel,
and recovering therefrom a mixture containing a dimer of
isobutylene.
2. A process for selectively dimerizing isobutylene which consists
essentially of contacting the mixture of C.sub.4 mono-olefins
containing isobutylene under dimerization conditions with a
sulfided catalyst composition consisting essentially of 0.5 to 20
weight percent of nickel and fluorine on an acidic amorphous
silica-alumina support, the maximum concentration of fluorine being
5.0 weight percent of said catalyst composition, said support
comprising from 50 to 90 weight percent silica, said sulfided
catalyst containing at least 0.5 mol of sulfur per mol of nickel,
and recovering therefrom a mixture containing a dimer of
isobutylene.
3. The process of claim 2 wherein contact between the C.sub.4
olefin mixture and catalyst composition is conducted at a liquid
weight hourly space velocity in the range of 0.5 to 2.8.
4. The process of claim 3 wherein the C.sub.4 feed mixture is a
liquid, the temperature in said dimerization zone is maintained in
the range of 70.degree. to 300.degree. F., and the pressure in said
dimerization zone is maintained in the range of 70 to 600 psig.
5. The process of claim 3 wherein the C.sub.4 olefin feed is a
vapor, the temperature of the dimerization zone is maintained in
the range of 300.degree. to 480.degree. F., and the pressure in
said dimerization zone is maintained in the range of 600 to 1,200
psig.
Description
BACKGROUND OF THE INVENTION
It is known that olefins, particularly mono 1-olefins, can be
polymerized with nickel supported on a material such as
silica-alumina. In such conventional processes, sulfur is
considered as a catalyst poison and special process steps are taken
to prevent its presence in the polymerization zone. The performance
of such catalysts in the dimerization of olefins can be judged by
consideration of the olefin conversion under desired process
conditions of temperature, pressure, space velocity and the yield
of the desired dimer. It is known that when conventional catalyst
compositions such as the catalyst composition described above are
employed in the dimerization of a feed comprising a mixture of
olefins, a mixture of polymer products is obtained, comprising
dimers, trimers, tetramers, and the like, of each of the olefins
present in the feed.
The catalytic alkylations of paraffinic hydrocarbons involves the
addition of an isoparaffin such as isobutane containing a tertiary
hydrogen and an olefin such as butene-1 or butene 2 to prepare
alkylate rich in highly branched C.sub.8 paraffins which have high
research and motor octane numbers. A conventional feed source of
such alkylation processes are C.sub.4 refinery streams containing a
mixture of isobutylene, butene-1, butene-2, n-butane, isobutane,
and perhaps minor concentrations of propylene, propane, butadiene,
and the like. In the sulfuric acid alkylation of isobutane to
produce a high octane gasoline component, isobutylene is not
particularly effective. Isobutylene tends to give the poorest
products, lowest yields, and highest acid consumption. Although not
desirable as a feed component to a sulfuric acid alkylation
process, it is known that isobutylene can be polymerized to form a
high octane gasoline blending component. Therefore, in order to
improve the sulfuric acid alkylation of isobutane in any C.sub.4
refinery stream while maximizing the production of high octane
gasoline blending components, it is desirable to provide a process
whereby the concentration of isobutylene in the alkylation process
feed is substantially reduced and the gasoline blending
characteristics of the separated isobutylene fraction substantially
improved.
Accordingly, an object of the invention is to provide an improved
process for separating isobutylene from the C.sub.4 hydrocarbon
feed to a sulfuric acid alkylation process.
Another object of the invention is to provide an improved catalyst
and process for selectively polymerizing isobutylene contained in a
C.sub.4 olefin mixture.
Yet another object of the invention is to provide an improved
process for maximizing the gasoline octane blending characteristics
of a C.sub.4 hydrocarbon feed mixture.
Other objects, advantages and features of the invention will be
readily apparent to those skilled in the art from the following
description and appended claims.
SUMMARY OF INVENTION
By the invention, isobutylene contained in a C.sub.4 mono-olefin
mixture is selectively polymerized in the presence of a sulfided
Group VI or Group VIII metal and an acidic amorphous silica-alumina
catalyst composition to form a dimer of isobutylene. The product
isobutylene dimer is valuable as a gasoline blending component with
its blending octane numbers being substantially higher than those
measured octane numbers of the product dimer. The isobutylene dimer
can also be hydrogenated to obtain a high octane gasoline blend
component.
DESCRIPTION OF THE INVENTION
The catalyst employed in the novel selective dimerization process
is a presulfided Group VI or Group VIII metal deposited on an
acidic amorphous silica-alumina support. The concentration of the
Group VI or Group VIII metal can range from 0.5 to 20 percent by
weight of the catalyst composition. The amorphous support is in
particulate form, is acidic and can comprise from 50 to 90 weight
percent silica with the remainder being alumina. Normally the
particle size of the support will range from one thirty-second inch
to one-eighth inch in diameter. In addition, the catalyst
composition can contain from 0 to 5.0 weight percent fluorine.
In preparation of the catalyst composition the amorphous
silica-alumina support can be impregnated with a Group VI or Group
VIII metal compound, e.g., an inorganic salt. A preferred method of
impregnation involves contacting the support with a solution of the
inorganic salt. The support optionally can contain fluorine or the
fluorine ion can be impregnated into the silica-alumina with the
metal. The salt is then converted to the oxide after drying by
calcining in an oxygen-containing atmosphere at a temperature in
the range of 900.degree. F. to 1,300.degree. F. for a period
ranging from 0.5 to 48 hours.
The calcined catalyst composition is then subjected to a
presulfiding step whereby the oxide is substantially completely
converted to the sulfide. Typically, this procedure comprises
treating the calcined catalyst composition with a sulfiding gas
such as a mixture of hydrogen and hydrogen sulfide at temperatures
of about 300.degree. to 750.degree. F. or more and at a pressure
ranging from atmospheric to 3,000 psig. In addition to hydrogen
sulfide, other sulfiding agents such as the lower molecular weight
mercaptans and organic sulfides can be utilized. The catalyst
composition can be heated to the presulfiding temperature in the
presence of hydrogen before contacting the catalyst with the
sulfur. The presulfiding treatment is continued until the catalyst
composition contains at least 0.5, preferably from 0.6 to 0.85, mol
of sulfur per mol of the Group VI or Group VIII metal as the
metallic sulfide. The catalyst composition can be used in the
dimerization process in the form of pellets, extrusions, granules
or powder.
The process of the invention is applicable to the selective
dimerization of isobutylene contained in a mixture of C.sub.4
mono-olefins. Although not to be limited thereto, the invention is
particularly applicable to the selective dimerization of
isobutylene contained in a C.sub.4 hydrocarbon refinery stream from
a fluid catalytic cracking unit with the concentration of
isobutylene normally ranging from 5 to 25 weight percent of the
mixture. It will be appreciated by those skilled in the art that
the selective dimerization process is also applicable to feed
mixtures derived from other sources, such as the sulfuric acid
extracted isobutylene which has subsequently been mixed with other
C.sub.4 mono-olefins.
The olefin mixture which is employed as feed to the dimerization
process should be substantially free of nitrogen and contain a
controlled concentration of sulfur. The concentration of sulfur in
the feed should be less than 225 ppm, preferably less than 50 ppm,
and can be controlled by a conventional caustic washing step. The
concentration of nitrogen in the hydrocarbon feed should not exceed
4 ppm and preferably no more than 1 ppm and can be controlled by
subjecting the hydrocarbon feed to a conventional nitrogen
separation step such as an acid wash.
The novel dimerization process can be conducted in the liquid phase
or the vapor phase. Liquid weight hourly space velocities in the
range of 0.5 to 2.8 are employed with space velocities in the range
of 1.0 to 2.5 being preferred. Contact between the catalyst
composition and the hydrocarbon feed can be effected in a fixed bed
or a fluidized bed.
The pressure in the dimerization zone is normally maintained in the
range of 70 to 600 psig, preferably 400 to 600 psig, to maintain a
liquid phase hydrocarbon operation. When conducting the
dimerization reaction in the vapor phase higher pressures of 600 to
1,200 psig are preferred to sustain a dense phase operation. A
liquid phase operation is used at temperatures in the range of
70.degree. to 300.degree. F. (preferably 140.degree. to 285.degree.
F.). A vaporous hydrocarbon phase operation would occur at a
reaction temperature above 300.degree. F., temperatures as high as
480.degree. F. may be employed.
The term "selective dimerization" as employed in the description of
the inventive process refers to the selectivity of the catalyst to
dimerize at least 50 weight percent of the isobutylene in the
presence of normal butenes with less than 15 weight percent of the
normal butenes being polymerized. It is within the scope of the
invention, however, to include other olefins such as propylene or
pentenes in the feed to the dimerization zone. Products of the
reaction in those instances where such other olefins are contained
in the feed may also include polymers of such olefin monomers. It
has been observed that when the novel dimerization process using a
presulfided 3.0 weight percent nickel and 2.0 weight percent
fluorine deposited on Triple A silica-alumina catalyst, is applied
to a C.sub.4 hydrocarbon feed mixture containing less than 15
weight percent isobutylene and more than 30 weight percent normal
butenes that at least 75 percent of the isobutylenes are
polymerized and less than 15 percent of the normal butenes are
polymerized.
The polymerization products of the novel process as applied to a
C.sub.4 mono-olefin feed mixture are substantially dimers, normally
greater than 60.0 weight percent, with essentially the remaining
polymer products being trimers. The polymerization products can be
separated from the remainder of the hydrocarbon feed by
fractionization. The separated polymer comprising substantially a
dimer of isobutylene can be used directly as a high research octane
gasoline blending component or can be hydrogenated by a
conventional process to obtain a high research and motor octane
gasoline blending component, as subsequently described.
The novel selective dimerization catalyst compositions are
effective for long periods of time without the necessity of
regeneration. It has been observed, for example, that after 45 days
of operation, a catalyst composition comprising a presulfided 3.0
weight percent nickel and 2.0 weight percent fluorine on a Triple A
silica-alumina support containing 0.79 mol of sulfer per mol of
nickel was capable of selectively dimerizing 95 percent of the
isobutylene contained in a C.sub.4 mono-olefin feed mixture. The
liquid feed mixture contained 10 weight percent isobutylene and the
process was conducted at a temperature of 260.degree. F., a
pressure of 600 psig, and a liquid weight hourly space velocity of
1.0. Aging of the catalyst in the selective dimerization of
isobutylene is such that at least two month operating cycles
without regeneration are obtainable with a feed containing 50 ppm
sulfur.
The isobutylene dimer having clear research and motor octane
numbers normally ranging from 101 to 102 and 84 to 85,
respectively, also has a high research octane blending value when
blended with other conventional gasoline blend components,
particularly in those instances where a low concentration of lead
is to be employed in the finished blend. The clear blending values
of the product polymer normally are 110-115 and about 89 for the
research and motor octane members, respectively. In those instances
where the concentration of lead in the finished blend is to exceed
0.5 gram per gallon, an improvement in research and motor octane
values can be obtained by hydrogenation of the dimer product prior
to blending the hydrogenation product with other gasoline blend
components.
The following examples are presented to illustrate objects and
advantages of the invention. It is not intended, however, to limit
the invention to specific embodiments illustrated therein.
EXAMPLE 1
This example illustrates the selective dimerization of isobutylene
contained in a C.sub.4 hydrocarbon feed mixture having the
following composition:
Weight Percent ______________________________________ Propane 0.26
Propylene 0.03 I-Butane 37.39 N-Butane 14.24 I-Butylene 10.16
Butene-1 9.65 Trans Butene-2 13.70 Cis Butene-2 10.12 I-Pentane
3.91 N-Pentane 0.12 2 Methyl-1 Butene 0.14 Cis Pentene-2 0.28
______________________________________
The C.sub.4 hydrocarbon feed mixture containing 182 parts per
million (ppm) sulfur was continuously passed over a 3.sup.A
molecular sieve drier to remove water and low molecular weight
nitrogen compounds such as ammonia and then to a dimerization zone
containing 144.5 grams of a catalyst composition presulfided by a
procedure hereafter described at a liquid weight hourly space
velocity of 1.0 for a period of 1 day. This run was conducted after
the catalyst composition had been employed in the selective
dimerization of isobutylene for a period of 45 days.
The catalyst composition comprised 3.0 weight percent nickel and
2.0 weight percent fluorine on a Triple A silica-alumina support
which had been sulfided so as to contain 0.79 mol of sulfur per mol
of nickel. The Triple A silica-alumina support comprises 75 weight
percent silica and 25 weight percent alumina. The support having a
particle size of 10 to 20 mesh had a surface area of 470 square
meters per gram, a pore volume of 0.83 cc per gram and an average
pore diameter of 71.sup.A. Its acidity was measured by ammonia
absorption at 350.degree. F. and was equal to 0.505
milliequivalents of ammonia per gram.
The catalyst composition was presulfided by a procedure whereby the
vessel containing the catalyst composition was pressured to 600
psig with hydrogen. It was heated at a rate of 50.degree. to
75.degree. F./Hr. in the presence of hydrogen to 650.degree. F. and
held at 650.degree. F. for a period of 1 hour. The presulfiding was
conducted at 650.degree. F. and 600 psig with carbon disulfide
dispersed in a pure grade heptane at 1 LWHSV. The concentration of
sulfur in the heptane was 3,000 parts per million. The presulfiding
was conducted for a period of 22 hours and in the presence of
hydrogen passing through the presulfiding zone at the rate of 6,000
standard cubic feet per hour per barrel of sulfiding blend.
The dimerization was conducted at a temperature in the range of
250.degree. to 266.degree. F. and at a pressure of 600 lbs. per
square inch gauge (psig).
Analysis of the product being continuously withdrawn from the
dimerization zone showed that 23.1 weight percent of the olefins
charged had been polymerized with 83.2 percent of the isobutylene
having been polymerized and 4.8 percent of the normal butenes
having been polymerized. Further analysis of the polymer product
indicated that 71.9 weight percent of the polymer product comprised
dimers and 28.1 weight percent of the product comprised trimers.
The polymer product had an API gravity of 59.3 and an octane number
of 100.9 (RON clear).
The hydrocarbon C.sub.3 - C.sub.4 product separated from the
polymer product has the following composition:
Weight Percent ______________________________________ Propylene 0.3
Propane 0.4 Isobutane 44.9 Butene-1 9.4 Isobutylene 2.0 N-Butane
15.1 Trans-2-Butene 16.5 Cis-2-Butene 11.3
______________________________________
EXAMPLE 2
In this example, the catalyst composition of Example 1 presulfided
by the procedure described therein was employed in the selective
dimerization of isobutylene contained in a sulfur-free C.sub.4
hydrocarbon feed mixture having the following composition:
Weight Percent ______________________________________ Isobutane
52.0 Butene-1 9.6 Isobutylene 10.3 Cis Butene-2 28.1
______________________________________
The C.sub.4 hydrocarbon mixture containing 56 parts per million of
water was passed to a dimerization zone containing the catalyst
composition of Example 1 at a liquid weight hourly space velocity
of 2.0. A temperature of 235.degree. F. and a pressure of 400 psig
were maintained in the dimerization zone. The dimerization process
was conducted continuously for a period of 1 day after the catalyst
composition had been employed in the selective dimerization of
isobutylene for a period of 34 days with feeds containing from 0 to
as much as 225 ppm sulfur. For the most part, however, the feed
contained 0 ppm sulfur.
Analysis of the product being continuously withdrawn from the
dimerization zone showed that 85.9 weight percent of the
isobutylene had been polymerized and 4.3 weight percent of the
normal butenes had been polymerized. Further analysis of the
polymer product indicated that 71.1 weight percent of the product
consisted of dimers, 27.3 weight percent consisted of trimers and
only 1.6 weight percent of the polymer product consisted of
tetramers. The polymer product had an API gravity of 60.9, a
research octane number of 100.9 (clear) and a distillation range as
follows:
Temperatures, Degrees F. ______________________________________ IBP
119 10% 219 50% 242 90% 355 EP 401
______________________________________
The hydrocarbon C.sub.4 mixture separated from the polymer product
had the following analysis:
Weight Percent ______________________________________ Isobutane
58.3 Butene-1 9.8 Isobutylene 1.6 N-Butane 0.1 Trans Butene-2 1.7
Cis Butene-2 28.5 ______________________________________
This example demonstrates the effectiveness of the novel
dimerization process to selectively dimerize isobutylene in the
presence of water with the hydrocarbon feed being sulfur-free.
EXAMPLE 3
In this example, the C.sub.4 hydrocarbon feed mixture of Example 1
was employed in the novel isobutylene dimerization process using a
6.0 weight percent nickel, 2.0 weight percent fluorine and a Triple
A silica-alumina support catalyst composition. The catalyst
composition was presulfided using the procedure cited in Example 1
with the exception that the carbon disulfide concentration in the
heptane consisted of 6,000 parts per million sulfur. The
presulfided catalyst contained 0.83 mol of sulfur per mol of
nickel.
The C.sub.4 hydrocarbon mixture was continuously passed to a
dimerization zone containing the catalyst composition at a liquid
weight hourly space velocity of 1.0. A dimerization temperature of
243.degree. F. and a pressure of 600 psig was maintained throughout
the 1 day run.
Analysis of the product being continuously withdrawn from the
dimerization zone showed that 75.9 weight percent of the
isobutylene had been polymerized and 4.4 weight percent of the
normal butenes had been polymerized. Further analysis of the
polymer product indicated that 69.3 weight percent of the product
comprised dimers, 28.6 weight percent comprised trimers and only
2.1 weight percent comprised tetramers. The polymer product had an
API gravity of 61.1 and a research octane number of 101.1 (clear).
The hydrocarbon C.sub.3 - C.sub.4 mixture separated from the
polymer product had the following analysis:
Weight Percent ______________________________________ Propylene .2
Propane .3 Isobutane 44.5 Butene-1 9.8 Isobutylene 2.8 N-Butane
15.0 Trans-2-Butene 16.2 Cis-2-Butene 11.1
______________________________________
Although the invention has been described with reference to
specific materials, embodiments and details, various modifications
and changes, within the scope of this invention will be apparent to
one skilled in the art and are contemplated to be embraced in the
invention.
* * * * *